EP1496999B1 - Activated oxidizing vapor treatment system and method - Google Patents

Activated oxidizing vapor treatment system and method Download PDF

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Publication number
EP1496999B1
EP1496999B1 EP03724259A EP03724259A EP1496999B1 EP 1496999 B1 EP1496999 B1 EP 1496999B1 EP 03724259 A EP03724259 A EP 03724259A EP 03724259 A EP03724259 A EP 03724259A EP 1496999 B1 EP1496999 B1 EP 1496999B1
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EP
European Patent Office
Prior art keywords
vapor
oxidant
set forth
chemical
further including
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP03724259A
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German (de)
English (en)
French (fr)
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EP1496999A1 (en
Inventor
Iain F. Mcvey
Lewis I. Schwartz
Michael A. Centanni
Gerald E. Mcdonnell
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Steris Inc
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Steris Inc
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours
    • A61L2/202—Ozone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours
    • A61L2/208—Hydrogen peroxide
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/02—Chemical warfare substances, e.g. cholinesterase inhibitors

Definitions

  • the present invention relates to the art of treating articles with highly reactive oxidant vapors. It finds particular application in conjunction with deactivating biological and chemical warfare agents, such as blistering agents (e.g., mustard gas), acetyl cholinesterase inhibitors (e.g., nerve gas), and biotoxins (e.g., botulinum toxin) and will be described with particular reference thereto. However, it is to be appreciated, that the present invention will find application in conjunction with the oxidation of other substances.
  • biological and chemical warfare agents such as blistering agents (e.g., mustard gas), acetyl cholinesterase inhibitors (e.g., nerve gas), and biotoxins (e.g., botulinum toxin) and will be described with particular reference thereto.
  • blistering agents e.g., mustard gas
  • acetyl cholinesterase inhibitors e.g., nerve gas
  • biotoxins e.g., botulinum toxin
  • Liquid oxidants have been developed which can deactivate biological warfare agents. See, for example, U.S. Patent No. 6,245,957 to Wagner, et al.
  • a strong oxidant solution is sprayed as a liquid or foam onto equipment in the field which is or has potentially been contaminated with biological and chemical warfare agents. After treatment, the solution is rinsed from the equipment with water, which can be permitted to flow onto the ground, as it is nontoxic.
  • the liquid Wagner solution has drawbacks. First, it is difficult for liquids to penetrate crevices, fine cracks, ducts, and partially protected or lapping parts. Second, in enclosed spaces, such as in the interior of airplanes and buildings, cleanup and disposal of the liquid solution can be problematic. Third, liquids can damage some equipment, such as electronic or electrical equipment.
  • the present application delivers the strong oxidant to the surfaces to be decontaminated in a vapor phase to facilitate penetration and cleanup.
  • biological and chemical warfare agent residues are deactivated by oxidation with a strong oxidant in the vapor phase.
  • the strong oxidant includes a peroxy compound.
  • An alkaline gas is added to the vapor phase oxidant to adjust a pH of the vapor phase oxidant.
  • an apparatus for deactivating biological or chemical warfare agent residue includes a means for subjecting an item bearing the warfare agent residue in an enclosure to a strong oxidant and an alkaline gas to adjust a pH of the oxidant.
  • the strong oxidant includes a peroxy compound and is in a vapor phase.
  • the means for subjecting includes a source of liquid oxidant.
  • a vaporizing means is connected with the source of liquid oxidant and with the enclosure for vaporizing the liquid oxidant and supplying the oxidant vapor to the enclosure.
  • a means provides an alkaline gas in vapor, mist, or fog form to the enclosure.
  • One advantage of the present invention resides in its improved penetration.
  • Another advantage of the present invention resides in its ease of cleanup.
  • Another advantage resides in compatibility with electrical equipment.
  • the invention may take form in various components and arrangements of components, and in various steps and arrangements of steps.
  • the drawings are only for purposes of illustrating a preferred embodiment and are not to be construed as limiting the invention.
  • a treatment enclosure 10 receives or is itself part of the structure potentially contaminated with biologically active substances such as biological or chemical warfare agents to be treated with vapor oxidant compounds.
  • biologically active substances include pathogens, biotoxins, prions, chemical agents such as nerve gas or blistering agents, and the like.
  • the treatment enclosure in one embodiment, is a chamber that is adapted to receive items to be treated and then sealed.
  • the enclosure includes the interior of a warehouse, room, aircraft or other vehicle, tent, or the like which is or whose surfaces or items contained in the enclosure are to be treated.
  • a warfare agent oxidizing means A includes a pump 12 that draws the environmental gas, typically air, from the enclosure through an optional biological and chemical hazard filter 14 or other means for preventing contamination in the enclosure from escaping and preferably through a dryer 16.
  • the dryer also includes a catalyst that breaks down the hydrogen peroxide vapor to water for removal by the dryer.
  • the blower blows the filtered and dried air into a vaporizer 18, which vaporizes a liquid oxidant compound from a liquid oxidant supply 20.
  • the vapor is blown through another optional biological contaminant filter 22 or other means for preventing contamination in the enclosure from escaping into the chamber 10.
  • the output of the vaporizer is branched or fed to a manifold that feeds the oxidant vapor into the enclosure from a plurality of locations.
  • additional fans or blowers 24 are placed in the enclosure to circulate the vapor and improve uniformity of concentration and distribution of the vapor.
  • the preferred oxidant liquid includes peroxy compounds such as hydrogen peroxide and peracetic acid. The use of other oxidants such as hypochlorites, solutions of ozone, and the like are also contemplated.
  • the oxidant compound is mixed with an alcohol to generate an alcohol vapor which functions as a cosolvent.
  • the temperature of the structure is preferably raised to 70° C which allows extraction of the agent from the material and facilitates reaction with the oxidant vapor. Moreover, higher temperatures permit higher concentrations of oxidant vapor without condensation problems. Of course, when plastics or temperature sensitive electronics are involved, temperatures of 45°-60° C may be preferred.
  • a chemical delivery means system B delivers other chemistry in a vapor, mist, or fog form directly into the enclosure 10.
  • the delivery means B includes a source 42 of other chemical vapor, mist, or fog.
  • the other chemistry delivery system includes filters, blowers, and vaporizers, analogous to those described for the oxidant vapor.
  • a liquid chemical is sprayed with a misting nozzle or fogged with a fogger directly into the enclosure.
  • a reservoir or cylinder of the other chemical in gaseous form is provided.
  • the other chemistry in one embodiment is selected (1) to activate the oxidant vapor to a higher oxidation potential, (2) to increase the number and diversity of reactive species, (3) to precondition the target substances to make them more susceptible to attack by the oxidant vapor, or (4) to react with the oxidant vapor to form an intermediate compound that attacks all or some of the target substances.
  • the oxidant vapor is hydrogen peroxide in a concentration of 25-75%, with about 50% preferred.
  • the other chemistry includes short alkene chains and water vapor, which interacts with the peroxide vapor to form a number of radical species, such as singlet pairs of oxygen, methyl radicals (CH 3 - ), hydroxyl radicals (OH - ), hydroperoxy radicals (OOH - ), and others.
  • the other delivery system delivers ozone, aldehydes, peroxy carboxylic acid, or the like to the chamber in vapor, mist, or fog.
  • UV light sources are used, in addition to or instead of, the chemical delivery system to enhance the reactive species.
  • the other chemistry includes a condensable solvent vapor, mist, or fog that is miscible with water and produces a solution with reduced polar properties is condensed on the target substance.
  • Suitable solvents include tertiary butyl alcohol (tBuOH), formic acid, peracetic acid, other alcohols, acetone, or acetyl nitrite.
  • the other chemistry adjusts pH.
  • acetic or formic acid is preferred.
  • Ammonia is preferred for raising the pH.
  • strong oxidants have a low pH which is advantageously raised to near neutral.
  • FIGURE 1 Although only a single other chemistry delivery system is illustrated in FIGURE 1, it is to be appreciated that individual delivery systems can be provided for the various above-discussed other chemistries.
  • a control 34 controls the other chemistry delivery system or means B and the peroxy vapor delivery system or means A.
  • the peroxy vapor and other chemistry are delivered concurrently into the enclosure.
  • the other chemistry is added to the enclosure first to precondition the biologically active substances. For example, injecting a cosolvent vapor and allowing it to condense prior to the hydrogen peroxide for partially dissolving or otherwise making biologically active substances that are not soluble in the oxidant vapor more readily penetrated by the oxidant vapor are contemplated.
  • the oxidant vapor is added to the enclosure first to establish equilibrium and start deactivating the biologically active substances that are more readily oxidized. Then the other chemistry is added to boost the reactivity of the oxidant vapor or to generate an intermediate vapor compound to attack the remaining biologically active substances.
  • a blower 12a draws atmospheric air from an enclosure 10a through a biologically active substance exit inhibiting means 14a such as a filter or valve and a dryer 16a.
  • the blower blows the atmospheric gases through a vaporizer 18a that vaporizes a peroxy liquid, preferably hydrogen peroxide from a source 20a.
  • the peroxy vapor is passed to a mixing chamber 40a where the other chemistry delivery means B mixes the peroxy vapor with the other chemistry from a source 42.
  • the mixing chamber 40 adds water vapor and short chain alkene vapor, aldehyde vapor, peroxycarboxylic acid vapor, or the like, to the peroxy vapor to form singlet oxygen, hydroperoxy, and other reactive radicals.
  • solvents or pH adjusting compounds are mixed with the oxidant vapor in the mixing chamber 40a.
  • the other chemistry reacts with the peroxy vapor to form an intermediate compound as described above.
  • the modified vapor is passed through a biologically active substance escape inhibiting means 22a, such as a filter or check valve, into the enclosure 10a .
  • the means 14a and 22a prevent contamination in the enclosure from migrating into the lines of the vapor delivery system.
  • another chemistry delivery system B' delivers a preconditioning vapor, mist, or fog, ammonia gas, or solvent vapor, as described above, directly into the enclosure or into the mixing chamber 40a.
  • a blower 12b blows the atmospheric air from an enclosure 10b through a vaporizer 18b of the oxidant vapor means A.
  • the output of the vaporizer is split between one path 50, which delivers the vapor directly to the enclosure 10b, and a second path 52 that delivers the vapor through a mixing chamber 40b of the other chemical delivery means B to the enclosure 10b.
  • Valves 54, 56 in lines 50 and 52 are controlled by a control system 34b for dynamically adjusting the proportion of the oxidant vapor that passes through the mixing chamber to control the amount of gaseous other chemistry introduced into the chamber.
  • a blower 12c pulls atmospheric air through a filter 14c and blows it into a vaporizer 18c.
  • the vaporizer 18c is connected with an oxidant liquid source 20c and at least one additional source of other chemistry 42c.
  • the oxidant liquid and the other chemistry(ies) are vaporized concurrently or sequentially in the vaporizer and fed to a treatment enclosure 10c.
  • one or more other chemicals are supplied in gaseous form and mix in the vaporizer with the oxidant and other chemical vapors. Air from the treatment enclosure can be recirculated as described in the first three embodiments.
  • the air and vapor pass from the chamber to an oxidant and other chemistry deactivator 16c such as a catalyst, and are blown through a biological filter 22c into the atmosphere.
  • an oxidant and other chemistry deactivator 16c such as a catalyst
  • the embodiments of FIGURES 1, 2, and 3 can also be configured in this flowthrough configuration.
  • HOO - and singlet oxygen 1 O 2 are potent oxidants.
  • Analogous species and other potent oxidants can be delivered using gas phase delivery.
  • the hydrogen peroxide makes contact with a surface, it transfers enough energy to the peroxide molecule for it to decompose into hydroxyl radicals.
  • H 2 O 2 + M ⁇ 2HO - where M represents a collision with the biologically active substance, a wall, other object, other molecule, or the like.
  • hydroxyl radicals can go on to form other more reactive radicals by interactions with hydrogen peroxide and water vapor.
  • Hydroxyl radicals HO-, hydroperoxy radicals HOO-, and singlet oxygen 1 O 2 are all potent oxidants and are all present in hydrogen peroxide vapor to some degree.
  • the hydrogen peroxide can dissolve or absorb onto/into the biologically active substance (i.e., dissolve into a liquid droplet, or absorb onto a solid particle).
  • a cosolvent is added to the vapor and allowed to condense onto the surfaces of the equipment to be decontaminated.
  • the solvent is selected as good solvents for the biologically active substances.
  • cosolvent mixtures examples include: water and tert-butyl alcohol; water and acetonitrile; water, acetronitrile and isopropyl alcohol.
  • the composition of the condensate can be controlled to produce a liquid film on the surfaces to be decontaminated.
  • an alkaline gas soluble in the solvent mixture (ammonia for example)
  • the pH of the condensed cosolvent layer can also be controlled.
  • the presence of hydrogen peroxide in the condensate serves to lower the pH (35% aqueous H 2 O 2 solution has a pH of approx. 3-4) and the ammonia can be added to raise the pH to the optimum value of around 8-9.
  • suitable solvents include tetrahydrofuran, dimethylsulfoxide, acetone, acetaldehyde, propylene oxide, acetamide, diethylamine, and dimethoxyethane.
  • One way to enhance the generation of reactive radicals is by irradiating the enclosure with ultraviolet light at a wavelength that causes degradation of hydrogen peroxide.
  • the increased degradation increases the concentration of radical intermediaries and enhances the decontamination effect.
  • O 3 alkenes
  • RCHO aldehydes
  • halogens Cl 2 , Br 2
  • the addition of ozone increases the yield of radicals and the vapor stream: O 3 + h ⁇ O 2 + O*
  • atomic oxygen O * is not a radical (all its electrons have paired spins), but is highly reactive.
  • RCH CHR + O 3 ⁇ [intermediates] ⁇ HO - + HOO - This produces radicals from ozone with a higher yield.
  • alkyl peroxy radicals RCHO + HO - ⁇ RCO - + H 2 O RCO - + O 2 ⁇ RC (O) OO -
  • the product here is the alkyl peroxy radical, a radical of percarboxylic acid, i.e., if R is CH 3 , this radical is formed from peracetic acid, another strong oxidant.
  • Halogens are also suitable strong oxidants.
  • X is any halogen: X 2 + h ⁇ 2X - X - + HOOH ⁇ HX + HOO - X - + tBuOH ⁇ HX + tBuO - Where tBuOH - tert butyl alcohol is added as part of the cosolvent system.

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  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
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  • Business, Economics & Management (AREA)
  • Animal Behavior & Ethology (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Bakery Products And Manufacturing Methods Therefor (AREA)
EP03724259A 2002-04-24 2003-04-24 Activated oxidizing vapor treatment system and method Expired - Lifetime EP1496999B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US37585102P 2002-04-24 2002-04-24
US375851P 2002-04-24
PCT/US2003/013006 WO2003090875A1 (en) 2002-04-24 2003-04-24 Activated oxidizing vapor treatment system and method

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EP1496999A1 EP1496999A1 (en) 2005-01-19
EP1496999B1 true EP1496999B1 (en) 2006-08-02

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US (3) US7592500B2 (ja)
EP (1) EP1496999B1 (ja)
JP (1) JP4255385B2 (ja)
KR (1) KR100643594B1 (ja)
CN (1) CN1649647A (ja)
AT (1) ATE334729T1 (ja)
AU (1) AU2003231130B2 (ja)
CA (1) CA2482667C (ja)
DE (1) DE60307259T2 (ja)
ES (1) ES2270022T3 (ja)
IL (2) IL164761A0 (ja)
MX (1) MXPA04010345A (ja)
NZ (1) NZ535974A (ja)
WO (1) WO2003090875A1 (ja)

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AU2003231130A1 (en) 2003-11-10
IL164761A (en) 2007-12-03
AU2003231130B2 (en) 2006-04-06
DE60307259D1 (de) 2006-09-14
IL164761A0 (en) 2005-12-18
US8129579B2 (en) 2012-03-06
CA2482667A1 (en) 2003-11-06
EP1496999A1 (en) 2005-01-19
US20040057868A1 (en) 2004-03-25
US7592500B2 (en) 2009-09-22
NZ535974A (en) 2007-10-26
CN1649647A (zh) 2005-08-03
US20060252974A1 (en) 2006-11-09
ATE334729T1 (de) 2006-08-15
MXPA04010345A (es) 2005-02-17
US20090263501A1 (en) 2009-10-22
WO2003090875A1 (en) 2003-11-06
DE60307259T2 (de) 2007-07-19
JP2005523133A (ja) 2005-08-04
CA2482667C (en) 2009-06-30
ES2270022T3 (es) 2007-04-01
JP4255385B2 (ja) 2009-04-15
KR20040104635A (ko) 2004-12-10
KR100643594B1 (ko) 2006-11-10

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